CN110760802B - Energy storage ceramic film - Google Patents

Abstract

The invention relates to an energy storage ceramic thin film, the energy storage ceramic thin film comprises a metal substrate and a first metal layer, a second metal layer, a second metal oxide layer and a second metal oxide layer sequentially formed on the metal substrate Thin film; wherein, the material of the first metal layer is the same as that of the metal substrate; the surface of the first metal layer is also provided with the second metal in the second metal layer and the first metal layer An alloy layer formed by combining the first metals in the The energy storage ceramic thin film of the invention can reduce the surface roughness of the metal substrate and at the same time ensure the binding force, thereby simultaneously improving the energy storage performance and reliability of the energy storage ceramic thin film.

Description

Energy storage ceramic film

This application is a divisional application of the invention application with "Application No.: 201810848153.X, filing date: July 27, 2018, named: energy storage thin film and its preparation method".

technical field

The invention relates to the field of energy, in particular to an energy storage ceramic thin film.

Background technique

Traditional energy storage ceramic thin films include a substrate and a ceramic thin film. Generally, increasing the surface roughness of the substrate can increase the contact area between the ceramic thin film and the substrate and improve the bonding force. Moreover, when the substrate is used as an electrode, the increase of its surface roughness can also increase the capacitance of the ceramic thin film. However, the increase in the surface roughness of the electrode increases the defect concentration at the contact surface between the electrode and the ceramic film, thereby reducing the breakdown field strength and energy storage density of the energy storage ceramic film, which is not conducive to the improvement of energy storage performance. Therefore, reducing the surface roughness of the electrode is beneficial to improving the energy storage performance of the energy storage ceramic thin film. However, the decrease in the surface roughness of the electrode will lead to a significant decrease in the binding force between the electrode and the ceramic film, and the decrease in the binding force is also fatal to the energy storage ceramic film.

Contents of the invention

Based on this, it is necessary to address the above problems and provide an energy storage ceramic thin film, which has a strong binding force and can simultaneously improve the energy storage performance and reliability of the energy storage ceramic thin film.

An energy storage ceramic thin film, the energy storage ceramic thin film comprises a metal substrate and a first metal layer, a second metal layer, a second metal oxide layer and a second metal oxide sequentially formed on the metal substrate film;

Wherein, the material of the first metal layer is the same as that of the metal substrate;

The surface of the first metal layer is further provided with an alloy layer formed by combining the second metal in the second metal layer with the first metal in the first metal layer.

In one of the embodiments, the first metal layer and the second metal layer are deposited and formed by using a magnetic filter multi-arc ion plating method, and when the magnetic filter multi-arc ion plating method is used to deposit and form the second metal layer, The first metal in the first metal layer and the second metal in the second metal layer form the alloy layer.

In one embodiment, the surface roughness of the metal substrate is 10nm-400nm.

In one of the embodiments, the metal substrate has a thickness of 6 μm to 18 μm; and/or

The surface tension of the metal substrate is greater than or equal to 60 dynes.

In one embodiment, the thickness of the first metal layer is 20nm-40nm.

In one embodiment, the thickness of the second metal layer is 30nm-60nm.

In one of the embodiments, the thickness of the alloy layer is 5nm˜10nm.

In one embodiment, the thickness of the second metal oxide layer is 5nm˜10nm.

In one embodiment, the thickness of the second metal oxide thin film is 25 nm˜1.99 μm, and the grain size of the second metal oxide thin film is 30 nm˜300 nm.

In one embodiment, the metal substrate includes copper foil, the first metal layer includes a copper layer, the alloy layer includes a copper-titanium alloy layer, the second metal layer includes a titanium layer, and the second The metal oxide layer includes a titanium dioxide layer, and the second metal oxide film includes a titanium dioxide film.

In the energy storage ceramic thin film of the present invention, the first metal layer and the metal substrate are firmly combined according to the principle of similarity and compatibility, and the first metal layer and the second metal layer improve the combination through the alloy layer formed by the first metal and the second metal Strength, the second metal oxide layer is the oxide of the second metal layer, the bonding force between the two layers is strong, the second metal oxide thin film and the second metal oxide layer are the same material layer, and the bonding force is strong. Therefore, the energy storage ceramic thin film of the present invention can reduce the surface roughness of the metal substrate while ensuring the bonding force, thereby simultaneously improving the energy storage performance and reliability of the energy storage ceramic thin film.

Description of drawings

Fig. 1 is the structural representation of energy storage ceramic film of the present invention;

Fig. 2 is a schematic diagram of the principle of the magnetic filter multi-arc ion plating method of the present invention.

In the figure: 1. Vacuum arc source; 2. Ignition device; 3. Visual window; 4. Filtering magnetic field; 5. Focusing magnetic field; 6. Vacuum chamber; 10. Metal substrate; 11. Target material; 12. Electron; 13. Metal droplet; 14. Ion; 15. Metal atom; 20. First metal layer; 30. Alloy layer; 40. Second metal layer; 41. Second metal oxide layer; 42. Second metal Oxide film; 50, ceramic film.

Detailed ways

The energy storage ceramic thin film provided by the present invention will be further described below.

The preparation method of the energy storage ceramic thin film provided by the present invention comprises:

S1, providing a metal substrate;

S2, using the first simple metal as the first target material, depositing a first metal prefabricated layer on the metal substrate by using a magnetic filter multi-arc ion plating method, the material of the first metal prefabricated layer is compatible with the metal substrate The material of the bottom is the same;

S3, using the second metal simple substance as the second target material, depositing a second metal prefabricated layer on the first metal prefabricated layer by using a magnetic filter multi-arc ion plating method, and while depositing and forming the second metal prefabricated layer, An alloy prefabricated layer is formed between the first metal prefabricated layer and the second metal prefabricated layer, and the alloy prefabricated layer is an alloy formed by the first metal and the second metal;

S4, performing oxidation treatment on the second metal prefabricated layer to form a second metal oxide prefabricated layer on the surface layer of the second metal prefabricated layer;

S5, forming a second metal oxide prefabricated film on the second metal oxide prefabricated layer to obtain a prefabricated energy storage ceramic film;

S6, performing heat treatment on the prefabricated energy storage ceramic thin film to obtain an energy storage ceramic thin film.

In step S1, the metal substrate is used as an electrode, and the actual contact area between the first metal prefabricated layer and the electrode is related to the surface roughness of the metal substrate. The larger the surface roughness, the larger the actual contact area, and the larger the capacitance per unit geometric area. big. However, the increase in the surface roughness of the metal substrate will instead increase the defect concentration at the contact surface between the metal substrate and the first metal prefabricated layer, such as easily causing holes on the surface of the first metal prefabricated layer, thereby reducing the impact of the energy storage ceramic film. The penetration field strength and energy storage density are not conducive to the improvement of energy storage performance. Therefore, the surface roughness of the metal substrate is 10nm-400nm, which is conducive to improving the energy storage performance of the ceramic energy storage thin film.

The metal substrate can be rigid or flexible. Considering that the dielectric constant of the ceramic film is much higher than that of the polymer film, when the metal substrate is flexible, the flexibility of the energy storage ceramic film can be realized, so that it can replace the polymer film and be used in the film capacitor to realize the film Capacitors are developing towards the trend of miniaturization, multi-function and thinning. Preferably, the metal substrate has a thickness of 6 μm to 18 μm, has good flexibility, and can better realize the flexibility of the energy storage ceramic thin film.

The material of the metal substrate is not limited, as long as it has strong high-temperature oxidation resistance and conductivity, including copper foil, titanium foil, silver foil, gold foil, platinum foil, aluminum foil, nickel foil, chromium foil, and tin foil. It can also be one of copper alloy, titanium alloy, silver alloy, gold alloy, platinum alloy, aluminum alloy, nickel alloy, chromium alloy and tin alloy.

Considering that copper foil is the most cost-effective metal material in the electronics industry, its resistivity is 1.75×10 ^-8 Ω·m, second only to silver (1.65×10 ^-8 Ω·m), and its thermal conductivity is 401W/(m· K), second only to silver (420W/(m K)), and the price of copper is much lower than that of silver. Secondly, industrial copper foil is relatively mature. Copper foil is divided into rolled copper foil and electrolytic copper foil, and all of them have been electroplated to prevent oxidation and high temperature anti-oxidation, and will not oxidize when calcined in air. Therefore, the metal substrate is preferably copper foil.

The surface tension of the metal substrate ≥ 60 dynes, preferably the surface tension of the metal substrate > 60 dynes, the higher the surface tension of the metal substrate, the stronger the bonding force between the first metal layer and the metal substrate powerful.

The surface activity of the metal substrate can be increased by treating the surface of the metal substrate, thereby increasing the surface tension. Preferably, the treatment method is: firstly heat the metal substrate, set the temperature at 100°C to 300°C, keep it warm for 10 minutes to 30 minutes, and then use the Hall ion source to treat the flexible metal substrate, argon The gas flow is 20sccm~50sccm, the vacuum degree is 2.0×10 ^-2 Pa~6.0×10 ^-2 Pa, the Hall ion source voltage is 800V~2000V, the current is 0.5A~2A, and the processing time is 1 minute to 10 minutes .

Since the surface roughness of the metal substrate is 10nm-400nm, which is relatively low, the material of the first metal prefabricated layer deposited on the metal substrate in step S2 is the same as that of the metal substrate. According to the principle of similarity and compatibility, the combination of the first metal prefabricated layer and the metal substrate is stronger, which makes up for the problem of poor connection that may be caused by the reduced roughness of the metal substrate.

Considering that the metal substrate is preferably copper foil, the first metal prefabricated layer is preferably a copper prefabricated layer.

Due to the low particle energy during deposition by conventional magnetron sputtering, sol-gel process, etc., the bonding force between the first metal prefabricated layer and the metal substrate is poor. Therefore, the present invention uses a magnetic filter multi-arc ion plating method to deposit and form the first metal prefabricated layer on the metal substrate.

As shown in Figure 2, the device for magnetic filtering multi-arc ion plating of the present invention includes a vacuum arc source 1, a ignition device 2, a visible window 3, a filtering magnetic field 4 and a focusing magnetic field 5, and a metal substrate 10 is located in a vacuum chamber 6 . The method of magnetic filter multi-arc ion plating of the present invention is that the arc generated by arcing burns on the surface of the first simple metal target 11, so that the target 11 is liquefied to generate ions 14, electrons 12 and metal droplets 13, which are charged. The particles (ions 14 and electrons 12) are accelerated by the electric field and pass through the filter magnetic field 4, the charged particles move along the magnetic field lines, and the uncharged metal droplets 13 are filtered by the filter magnetic field 4. After filtering, the pure particles enter the vacuum chamber 6 through the focusing magnetic field 5 and are deposited on the metal substrate 10 by using the bias electric field applied to the metal substrate 10 . During this whole process, the electrons 12 are gathered and accelerated to form a moving electron cloud, and after the electron cloud is separated from the ions 14, a strong electric potential is formed between the two, and the ions 14 are extracted and deposited on the metal substrate 10 together with the electrons 12 , completing the magnetic filter multi-arc ion plating process to form the first metal prefabricated layer.

Because in the magnetic filtration multi-arc ion plating process, the accelerated electrons 12 constantly hit the surface of the metal substrate 10, producing metal atoms 15, which clean and activate the surface of the metal substrate 10, and make the surface of the metal substrate 10 active. Enhanced, so it has a strong binding force with the deposited first metal prefabricated layer. Moreover, the energy of the particles can be controlled by adjusting the extraction electric field and bias voltage. Therefore, the particle energy of the first metal prefabricated layer formed by the magnetic filter multi-arc ion plating method is an order of magnitude higher than the particle energy formed by methods such as magnetron sputtering. The prefabricated layer has a higher bonding force with the metal substrate and has higher reliability.

Preferably, the working atmosphere of the magnetic filter multi-arc ion plating method is argon gas, and Ar ⁺ generated after argon gas ionization hits the target under the action of an electric field. The flow rate of the argon gas is 20 sccm-50 sccm, and the vacuum degree is 2.0×10 ^-2 Pa-6.0×10 ^-2 Pa. The more Ar ⁺ in the chamber, the greater the kinetic energy generated, which is more conducive to the escape of target ions.

Preferably, the arc current of the magnetic filter multi-arc ion plating method is 45A to 60A, the drawn current is 7A to 11A, the bias voltage applied to the metal substrate is 5V to 10V, and the deposition time is 35 seconds to 65 seconds. Second. Further, the thickness of the deposited first metal prefabricated layer is 35nm-65nm.

Similarly, in step S3, a magnetic filter multi-arc ion plating method is used to deposit and form a second metal preformed layer on the first metal preformed layer. Moreover, the magnetic filter multi-arc ion plating method belongs to the ion plating film. When depositing and forming the second metal prefabricated layer, an alloy prefabricated layer of the first metal and the second metal is easily formed between the first metal prefabricated layer and the second metal prefabricated layer. In order to improve the bonding force between the first metal prefabricated layer and the second metal prefabricated layer.

Preferably, the working atmosphere of the magnetic filter multi-arc ion plating method is argon gas, and Ar ⁺ generated after argon gas ionization hits the target under the action of an electric field. The flow rate of the argon gas is 20 sccm-50 sccm, and the vacuum degree is 2.0×10 ^-2 Pa-6.0×10 ^-2 Pa. The more Ar ⁺ in the chamber, the greater the kinetic energy generated, which is more conducive to the escape of target ions.

Preferably, the arc current of the magnetic filter multi-arc ion plating method is 45A to 60A, the drawn current is 7A to 11A, the bias voltage applied to the metal substrate is 5V to 10V, and the deposition time is 60 seconds to 100 seconds. Second. Therefore, the bias voltage applied to the metal substrate generates an electric field, and under the action of the electric field, the charged second metal ion has a certain energy, such as Ti ⁴⁺ , which has an energy of 20eV under the action of an electric field of 5V, By controlling the energy of the ions, the formation of the alloy prefabricated layer of the first metal and the second metal and the thickness of the alloy prefabricated layer are controlled.

Further, the thickness of the deposited second metal prefabricated layer is 50nm-85nm, and the thickness of the formed alloy prefabricated layer is 10nm-15nm. At this time, the thickness of the first metal prefabricated layer is reduced to 25nm-50nm.

The second metal prefabricated layer may include titanium prefabricated layer, aluminum prefabricated layer, zirconium prefabricated layer, etc. Considering that the titanium dioxide ceramic film has a high breakdown field strength (> 1000kV/cm), although its dielectric constant is only about 120, but The energy storage density can reach 15J/cm ³ , and the use of titanium dioxide ceramic film can further increase the energy storage density of the energy storage ceramic film. Therefore, the second metal prefabricated layer is preferably a titanium prefabricated layer.

In step S4, the Hall ion source is preferably used to oxidize the second metal layer, the flow rate of oxygen is 50 sccm-80 sccm, the degree of vacuum is 5.0×10 ^-2 Pa-8.0×10 ^-2 Pa, Hall The ion source voltage is 1000V-2000V, the current is 0.6A-2A, and the oxidation treatment time is 10 minutes-20 minutes. Oxidizing the surface of the second metal prefabricated layer by high-energy oxygen Hall ions can oxidize the surface layer of the second metal prefabricated layer to form a second metal oxidized prefabricated layer. Since the second metal oxide prefabricated layer is an in-situ grown prefabricated layer, it has a strong bonding force with the second metal prefabricated layer and has high reliability.

Further, the thickness of the second metal oxide prefabricated layer obtained after the oxidation treatment is 10 nm to 15 nm, and at this time, the thickness of the second metal prefabricated layer is reduced to 40 nm to 70 nm.

Due to the limited thickness of the second metal oxide prefabricated layer obtained by the oxidation treatment, a second metal oxide prefabricated film is deposited again on the second metal oxide prefabricated layer through step S5, and the thickness of the second metal oxide prefabricated film is 40nm ~3.2 μm, the grain size of the second metal oxide prefabricated film is 20nm~200nm, and the film structure is dense. Because the composition of the second metal oxide prefabricated layer and the second metal oxide prefabricated film is the same, the bonding force between the second metal oxide prefabricated layer and the second metal oxide prefabricated film is strong, and the two constitute the prefabricated ceramic film, and then obtain A prefabricated energy storage ceramic thin film comprising a metal substrate, a first metal prefabricated layer, an alloy prefabricated layer, a second metal prefabricated layer, a second metal oxide prefabricated layer and a second metal oxide prefabricated thin film sequentially formed on the metal substrate.

In step S5, the method for forming the second metal oxide prefabricated film may be magnetron sputtering, magnetic filter multi-arc ion plating, or the like. When the magnetron sputtering method is adopted, the working atmosphere of the magnetron sputtering method is argon gas, the flow rate of the argon gas is 30sccm-120sccm, and the vacuum degree is 0.1Pa-0.5Pa. In the magnetron sputtering method, the power of the magnetron sputtering is 100W-200W, and the deposition time is 0.5 minutes-40 minutes.

Considering that the second metal prefabricated layer is preferably a titanium prefabricated layer, the second metal oxide prefabricated layer is a titanium dioxide prefabricated layer, and the second metal oxide prefabricated film is a titanium dioxide prefabricated film.

In step S6, heat treatment is performed on the prefabricated energy storage ceramic thin film, the temperature of the heat treatment is 300°C-500°C, and the time is 30 minutes-300 minutes. Heat treatment at 300° C. to 500° C. for 30 minutes to 300 minutes can cause the crystal lattice in the first metal prefabricated layer, the alloy prefabricated layer, the second metal prefabricated layer, the second metal oxide prefabricated layer and the second metal oxide prefabricated film to be distorted. A large number of non-equilibrium defects such as coordination, lattice reconstruction, impurities, and phase transitions disappear, and the internal stress is significantly reduced, and an energy storage ceramic film is obtained.

Preferably, argon is filled during heat treatment to prevent oxidation. The flow rate of the argon gas is 100sccm-200sccm, and the vacuum degree is 0.1Pa-1Pa.

The energy storage ceramic thin film obtained by the preparation method of the present invention has strong bonding force, the reasons are: first, the first metal layer and the metal substrate are made of the same material, and the bonding force between the two layers is strong according to the principle of similarity and compatibility; The filter multi-arc ion plating method deposits the first metal layer and the second metal layer on the metal substrate, and the deposited particles have high energy and strong binding force; third, through the magnetic filter multi-arc ion plating method, the first metal An alloy layer of the first metal and the second metal is formed between the first metal layer and the second metal layer, thereby improving the bonding force between the first metal layer and the second metal layer; fourth, the second metal oxide layer is the original metal oxide layer of the second metal layer The second metal oxide film has a strong binding force with the second metal layer; fifthly, according to the principle of similarity and compatibility, the second metal oxide film has a strong binding force with the second metal oxide layer.

The preparation method of the invention can be carried out in the same chamber, has high preparation efficiency, good microstructures such as crystallinity and grain size of the ceramic thin film, low internal stress, and improves the energy storage performance of the energy storage ceramic thin film.

As shown in FIG. 1 , the present invention also provides an energy storage ceramic thin film, which includes a metal substrate 10 and a first metal layer 20, an alloy layer 30, The second metal layer 40, the second metal oxide layer 41 and the second metal oxide film 42; wherein, the material of the first metal layer 20 is the same as that of the metal substrate 10, and the alloy layer 30 is An alloy layer formed by the first metal and the second metal. The second metal oxide layer 41 and the second metal oxide thin film 42 constitute the ceramic thin film 50 .

Preferably, the energy storage ceramic thin film is prepared by the above preparation method. Wherein, the first metal layer 20, the alloy layer 30, the second metal layer 40, the second metal oxide layer 41 and the second metal oxide film 42 are composed of the first metal prefabricated layer, the alloy prefabricated layer, the second metal prefabricated layer, The second metal oxide prefabricated layer and the second metal oxide prefabricated thin film are obtained after heat treatment, and have better crystal lattice, lower non-equilibrium defects and lower internal stress.

Preferably, the surface roughness of the metal substrate 10 is 10 nm˜0.4 μm.

Preferably, the metal substrate 10 has a thickness of 6 μm to 18 μm; and/or

The surface tension of the metal substrate 10 is greater than or equal to 60 dynes; and/or

The thickness of the first metal layer 20 is 20nm-40nm; and/or

The thickness of the second metal layer 40 is 30nm-60nm; and/or

The thickness of the alloy layer 30 is 5 nm to 10 nm; and/or

The thickness of the second metal oxide layer 41 is 5nm-10nm; and/or

The thickness of the second metal oxide thin film 42 is 25 nm˜1.99 μm, and the grain size of the second metal oxide thin film 42 is 30 nm˜300 nm.

Preferably, the metal substrate 10 includes copper foil, the first metal layer 20 includes a copper layer, the alloy layer 30 includes a copper-titanium alloy layer, the second metal layer 40 includes a titanium layer, and the second The metal oxide layer 41 includes a titanium dioxide layer, and the second metal oxide thin film 42 includes a titanium dioxide thin film.

In the energy storage ceramic thin film of the present invention, the first metal layer and the metal substrate are firmly combined according to the principle of similarity and compatibility, and the first metal layer and the second metal layer improve the combination through the alloy layer formed by the first metal and the second metal Strength, the second metal oxide layer is the oxide of the second metal layer, the bonding force between the two layers is strong, the second metal oxide thin film and the second metal oxide layer are the same material layer, and the bonding force is strong. Therefore, the energy storage ceramic thin film of the present invention can reduce the surface roughness of the metal substrate while ensuring the bonding force, thereby simultaneously improving the energy storage performance and reliability of the energy storage ceramic thin film.

Hereinafter, the energy storage thin film will be further described through the following specific examples.

Example 1:

A flexible and low-roughness copper foil is used as a substrate with a thickness of 6 μm and a surface roughness of 10 nm, placed in a vacuum chamber, and evacuated to 3×10 ^-3 Pa. The vacuum chamber is heated to 150°C, the holding time is 10min, filled with argon gas, the flow rate of argon gas is 20 sccm, the vacuum degree of the vacuum chamber is 2×10 ^-2 Pa, the Hall ion source is turned on, and the voltage of the Hall ion source is set to 1000V, current 0.5A, treatment for 1min, so that the surface tension of the copper foil reaches 60 dynes.

Keep the vacuum degree at 2.0×10 ^-2 Pa, the argon gas flow rate at 20 sccm, use metal copper as the target material, turn on the first magnetic filter multi-arc ion plating power supply, adjust the arc current to 50A, draw the current to 9A, and apply it to the copper foil The bias voltage is 5V, the deposition time is 35s, a copper prefabricated layer with a thickness of 35nm is formed on the copper foil, and the first magnetic filter multi-arc ion plating power supply is turned off. With metal titanium as the target material, turn on the second magnetic filter multi-arc ion plating power supply, adjust the arc current to 50A, draw the current to 10A, apply a bias voltage of 7V to the copper foil, and deposit for 60s to obtain a titanium prefabricated layer with a thickness of 50nm And a copper-titanium alloy prefabricated layer with a thickness of 10nm, at this time, the thickness of the copper prefabricated layer is reduced to 25nm.

Turn off the second magnetic filter multi-arc ion plating power supply and argon switch valve, open the oxygen valve, adjust the oxygen flow rate to 50 sccm, the vacuum degree to 5.0×10 ^-2 Pa, turn on the Hall ion source, the voltage is 1000V, and the current is 0.6A , the treatment time is 10min, the surface of the titanium prefabricated layer is oxidized to obtain a titanium dioxide prefabricated layer with a thickness of 10nm, and the thickness of the titanium prefabricated layer is reduced to 40nm at this time.

Turn off the Hall ion source and the oxygen valve, open the argon valve, adjust the argon flow rate to 30sccm, and the vacuum degree to 0.1Pa, turn on the magnetron sputtering power supply, adjust the power to 100W, and the deposition time to 30s to obtain titanium dioxide with a thickness of 40nm The prefabricated thin film, the grain size of the prefabricated titanium dioxide thin film is 20nm, and then the prefabricated energy storage ceramic thin film is obtained.

Turn off the magnetron sputtering power supply and the argon gas valve, increase the flow rate of argon gas to 100sccm, make the vacuum degree of the vacuum chamber 0.1Pa, heat the temperature to 300°C, and hold it for 30 minutes to eliminate the residual stress of the prefabricated energy storage ceramic film, An energy storage ceramic thin film is obtained. The energy storage ceramic thin film includes copper foil and sequentially formed on the copper foil are a copper layer, a copper-titanium alloy layer, a titanium layer, a titanium dioxide layer and a titanium dioxide film, wherein the titanium dioxide layer and the titanium dioxide film constitute the ceramic film.

Copper metal was deposited on the titanium dioxide film of the energy storage film as an upper electrode through a magnetron sputtering process, and the electrical performance test was carried out.

After testing, the thickness of the titanium dioxide film in the energy storage ceramic film is 25nm, the grain size of the titanium dioxide film is 30nm, the thickness of the titanium dioxide layer is 5nm, the thickness of the titanium layer is 30nm, the thickness of the copper-titanium alloy layer is 5nm, and the thickness of the copper layer is 5nm. The thickness is 20nm, and the binding force between each layer is 5B. The energy storage ceramic thin film is flexible, the minimum bending radius is 2 mm, the breakdown field strength is 2000 kV/cm, and the energy storage density is 35 J/cm ³ . After 1000 times of bending, the binding force between each layer is 5B, the energy storage density is 34.8J/cm ³ , and the retention rate is 99.5%, which can be applied in film capacitors.

Example 2:

A flexible and low-roughness copper foil is used as a substrate with a thickness of 10 μm and a surface roughness of 20 nm, placed in a vacuum chamber, and evacuated to 3×10 ^-3 Pa. The vacuum chamber is heated to 100°C, the holding time is 20min, filled with argon gas, the flow rate of argon gas is 30 sccm, the vacuum degree of the vacuum chamber is 3×10 ^-2 Pa, the Hall ion source is turned on, and the voltage of the Hall ion source is set to 800V, current 0.6A, treatment for 5min, so that the surface tension of the copper foil reaches 65 dynes.

Keep the vacuum degree at 3.0×10 ^-2 Pa, the argon gas flow rate at 30 sccm, use metal copper as the target material, turn on the first magnetic filter multi-arc ion plating power supply, adjust the arc current to 55A, draw the current to 10A, and apply it to the copper foil The bias voltage is 6V, the deposition time is 45s, a copper prefabricated layer with a thickness of 45nm is formed on the copper foil, and the first magnetic filter multi-arc ion plating power supply is turned off. With metal titanium as the target material, turn on the second magnetic filter multi-arc ion plating power supply, adjust the arc current to 45A, draw the current to 10A, apply a bias voltage of 8V to the copper foil, and deposit for 70s to obtain a titanium prefabricated layer with a thickness of 60nm And a copper-titanium alloy prefabricated layer with a thickness of 11nm, at this time, the thickness of the copper prefabricated layer is reduced to 34nm.

Turn off the second magnetic filter multi-arc ion plating power supply and argon switching valve, open the oxygen valve, adjust the oxygen flow rate to 60 sccm, the vacuum degree to 6.0×10 ^-2 Pa, turn on the Hall ion source, the voltage is 1200V, and the current is 0.7A , the treatment time is 15min, the surface of the titanium prefabricated layer is oxidized to obtain a titanium dioxide prefabricated layer with a thickness of 12nm, and the thickness of the titanium prefabricated layer is reduced to 48nm at this time.

Turn off the Hall ion source and the oxygen valve, open the argon valve, adjust the argon flow rate to 60sccm, and the vacuum degree to 0.4Pa, turn on the magnetron sputtering power supply, adjust the power to 120W, and set the deposition time to 1min to obtain titanium dioxide with a thickness of 80nm The prefabricated thin film, the grain size of the prefabricated titanium dioxide thin film is 80nm, and then the prefabricated energy storage ceramic thin film is obtained.

Turn off the magnetron sputtering power supply and the argon gas valve, increase the flow rate of argon gas to 150sccm, make the vacuum degree of the vacuum chamber 0.5Pa, heat the temperature to 400°C, and hold the temperature for 3h to eliminate the residual stress of the prefabricated energy storage ceramic film. An energy storage ceramic thin film is obtained. The energy storage ceramic thin film includes copper foil and sequentially formed on the copper foil are a copper layer, a copper-titanium alloy layer, a titanium layer, a titanium dioxide layer and a titanium dioxide film, wherein the titanium dioxide layer and the titanium dioxide film constitute the ceramic film.

Silver metal was deposited on the titanium dioxide film of the energy storage film as an upper electrode through a magnetron sputtering process, and the electrical performance test was carried out.

After testing, the thickness of the titanium dioxide film in the energy storage ceramic film is 50nm, the grain size of the titanium dioxide film is 120nm, the thickness of the titanium dioxide layer is 7nm, the thickness of the titanium layer is 40nm, the thickness of the copper-titanium alloy layer is 6nm, and the thickness of the copper layer is The thickness is 29nm, and the binding force between each layer is 5B. The energy storage ceramic thin film is flexible, the minimum bending radius is 5 mm, the breakdown field strength is 4000 kV/cm, and the energy storage density is 65 J/cm ³ . After 1000 times of bending, the binding force between each layer is 5B, the energy storage density is 64.7J/cm ³ , and the retention rate is 99.6%, which can be applied in film capacitors.

Example 3:

A flexible and low-roughness copper foil is used as a substrate with a thickness of 12 μm and a surface roughness of 80 nm, placed in a vacuum chamber, and evacuated to 3×10 ^-3 Pa. The vacuum chamber is heated to 300°C, the holding time is 30min, filled with argon gas, the flow rate of argon gas is 50 sccm, the vacuum degree of the vacuum chamber is 6×10 ^-2 Pa, the Hall ion source is turned on, and the voltage of the Hall ion source is set to 1500V, current 2A, treatment for 10min, so that the surface tension of the copper foil reaches 75 dynes.

Keep the vacuum at 6.0×10 ^-2 Pa, the argon gas flow rate at 50 sccm, use metal copper as the target material, turn on the first magnetic filter multi-arc ion plating power supply, adjust the arc current to 60A, draw the current to 11A, and apply it to the copper foil. The bias voltage is 10V, the deposition time is 65s, a copper prefabricated layer with a thickness of 65nm is formed on the copper foil, and the first magnetic filter multi-arc ion plating power supply is turned off. With metal titanium as the target material, turn on the second magnetic filter multi-arc ion plating power supply, adjust the arc current to 60A, draw the current to 11A, apply a bias voltage of 10V to the copper foil, and deposit for 100s to obtain a titanium prefabricated layer with a thickness of 85nm And a copper-titanium alloy prefabricated layer with a thickness of 15nm, at this time, the thickness of the copper prefabricated layer is reduced to 50nm.

Turn off the second magnetic filter multi-arc ion plating power supply and argon switch valve, open the oxygen valve, adjust the oxygen flow rate to 80sccm, the vacuum degree to 8.0×10 ^-2 Pa, turn on the Hall ion source, the voltage is 2000V, the current is 2A, The treatment time is 20 minutes to oxidize the surface of the titanium prefabricated layer to obtain a titanium dioxide prefabricated layer with a thickness of 15 nm. At this time, the thickness of the titanium prefabricated layer is reduced to 70 nm.

Turn off the Hall ion source and the oxygen valve, open the argon valve, adjust the argon flow rate to 120 sccm, the vacuum degree to 0.5 Pa, turn on the magnetron sputtering power supply, adjust the power to 200W, and the deposition time to 40min to obtain a film with a thickness of 3.2μm. The titanium dioxide prefabricated thin film has a grain size of 200nm, and then the prefabricated energy storage ceramic thin film is obtained.

Turn off the magnetron sputtering power supply and the argon gas valve, increase the flow rate of argon gas to 200 sccm, make the vacuum degree of the vacuum chamber 1 Pa, heat the temperature to 500 ° C, hold for 5 h, eliminate the residual stress of the prefabricated energy storage ceramic film, and obtain Energy storage ceramic film. The energy storage ceramic thin film includes copper foil and sequentially formed on the copper foil are a copper layer, a copper-titanium alloy layer, a titanium layer, a titanium dioxide layer and a titanium dioxide film, wherein the titanium dioxide layer and the titanium dioxide film constitute the ceramic film.

Platinum metal was deposited on the titanium dioxide film of the energy storage film as an upper electrode through a magnetron sputtering process, and the electrical performance test was carried out.

After testing, the thickness of the titanium dioxide film in the energy storage ceramic film is 1.99 μm, the grain size of the titanium dioxide film is 300 nm, the thickness of the titanium dioxide layer is 10 nm, the thickness of the titanium layer is 60 nm, the thickness of the copper-titanium alloy layer is 10 nm, and the copper layer The thickness is 40nm, and the binding force between each layer is 5B. The energy storage ceramic thin film is flexible, the minimum bending radius is 20 mm, the breakdown field strength is 2000 kV/cm, and the energy storage density is 25 J/cm ³ . After 1000 times of bending, the binding force between each layer is 5B, the energy storage density is 24.9J/cm ³ , and the retention rate is 99.8%, which can be applied in film capacitors.

Example 4:

A flexible and low-roughness copper foil is used as a substrate with a thickness of 18 μm and a surface roughness of 400 nm, placed in a vacuum chamber, and evacuated to 3×10 ^-3 Pa. The vacuum chamber is heated to 300°C, the holding time is 30min, filled with argon gas, the flow rate of argon gas is 40 sccm, the vacuum degree of the vacuum chamber is 4×10 ^-2 Pa, the Hall ion source is turned on, and the voltage of the Hall ion source is set to 800V, current 0.5A, treatment for 7 minutes, so that the surface tension of the copper foil reaches 65 dynes.

Keep the vacuum degree at 3.0×10 ^-2 Pa, the argon gas flow rate at 40 sccm, and use metal copper as the target material, turn on the first magnetic filter multi-arc ion plating power supply, adjust the arc current to 45A, draw the current to 7A, and apply it to the copper foil. The bias voltage is 6V, the deposition time is 50s, a copper prefabricated layer with a thickness of 50nm is formed on the copper foil, and the first magnetic filter multi-arc ion plating power supply is turned off. With metal titanium as the target material, turn on the second magnetic filter multi-arc ion plating power supply, adjust the arc current to 45A, draw the current to 7A, apply a bias voltage of 5V to the copper foil, and deposit for 100s to obtain a titanium prefabricated layer with a thickness of 60nm and a copper-titanium alloy prefabricated layer with a thickness of 10 nm, at this time, the thickness of the copper prefabricated layer is reduced to 40 nm.

Turn off the second magnetic filter multi-arc ion plating power supply and argon switch valve, open the oxygen valve, adjust the oxygen flow rate to 60sccm, the vacuum degree to 6.0×10 ^-2 Pa, turn on the Hall ion source, the voltage is 1500V, and the current is 1.2A , the treatment time is 10min, the surface of the titanium prefabricated layer is oxidized to obtain a titanium dioxide prefabricated layer with a thickness of 13nm, and the thickness of the titanium prefabricated layer is reduced to 47nm at this time.

Turn off the Hall ion source and the oxygen valve, open the argon valve, adjust the argon flow rate to 100 sccm, the vacuum degree to 0.3 Pa, turn on the magnetron sputtering power supply, adjust the power to 150W, and the deposition time to 30min to obtain a film with a thickness of 2.4μm. The titanium dioxide prefabricated thin film has a grain size of 150nm, and then a prefabricated energy storage ceramic thin film is obtained.

Turn off the magnetron sputtering power supply and the argon gas valve, increase the argon gas flow rate to 150sccm, make the vacuum degree of the vacuum chamber 0.5Pa, heat the temperature to 450°C, and hold the temperature for 4h to eliminate the residual stress of the prefabricated energy storage ceramic film. An energy storage ceramic thin film is obtained. The energy storage ceramic thin film includes copper foil and sequentially formed on the copper foil are a copper layer, a copper-titanium alloy layer, a titanium layer, a titanium dioxide layer and a titanium dioxide film, wherein the titanium dioxide layer and the titanium dioxide film constitute the ceramic film.

Platinum metal was deposited on the titanium dioxide film of the energy storage film as an upper electrode through a magnetron sputtering process, and the electrical performance test was carried out.

After testing, the thickness of the titanium dioxide film in the energy storage ceramic film is 1.49 μm, the grain size of the titanium dioxide film is 200 nm, the thickness of the titanium dioxide layer is 8 nm, the thickness of the titanium layer is 42 nm, the thickness of the copper-titanium alloy layer is 5 nm, and the copper layer The thickness of the layer is 30nm, and the binding force between each layer is 5B. The energy storage ceramic thin film is flexible, the minimum bending radius is 12 mm, the breakdown field strength is 2500 kV/cm, and the energy storage density is 30 J/cm ³ . After 1000 times of bending, the binding force between each layer is 5B, the energy storage density is 29.8J/cm ³ , and the retention rate is 99.5%, which can be applied in film capacitors.

Example 5:

A flexible low-roughness copper foil is used as a substrate with a thickness of 13 μm and a surface roughness of 250 nm, placed in a vacuum chamber, and evacuated to 3×10 ^-3 Pa. The vacuum chamber was heated to 200°C, the holding time was 25min, filled with argon gas, the flow rate of argon gas was 40 sccm, the vacuum degree of the vacuum chamber was 5×10 ^-2 Pa, the Hall ion source was turned on, and the voltage of the Hall ion source was set to 1200V, current 1.2A, treatment for 6min, so that the surface tension of the copper foil reaches 65 dynes.

Keep the vacuum degree at 2.5×10 ^-2 Pa, the argon gas flow rate at 25 sccm, use metal copper as the target material, turn on the first magnetic filter multi-arc ion plating power supply, adjust the arc current to 50A, draw the current to 9A, and apply it to the copper foil The bias voltage is 8V, the deposition time is 40s, a copper prefabricated layer with a thickness of 40nm is formed on the copper foil, and the first magnetic filter multi-arc ion plating power supply is turned off. With metal titanium as the target material, turn on the second magnetic filter multi-arc ion plating power supply, adjust the arc current to 55A, draw the current to 11A, apply a bias voltage of 10V to the copper foil, and deposit for 80s to obtain a titanium prefabricated layer with a thickness of 65nm And a copper-titanium alloy prefabricated layer with a thickness of 15nm, at this time, the thickness of the copper prefabricated layer is reduced to 25nm.

Turn off the second magnetic filter multi-arc ion plating power supply and argon switch valve, open the oxygen valve, adjust the oxygen flow rate to 70sccm, the vacuum degree to 7.0×10 ^-2 Pa, turn on the Hall ion source, the voltage is 1500V, and the current is 1.5A , the treatment time is 15min, the surface of the titanium prefabricated layer is oxidized to obtain a titanium dioxide prefabricated layer with a thickness of 13nm, and the thickness of the titanium prefabricated layer is reduced to 52nm at this time.

Turn off the Hall ion source and the oxygen valve, open the argon valve, adjust the argon flow rate to 110 sccm, the vacuum degree to 0.4Pa, turn on the magnetron sputtering power supply, adjust the power to 170W, and the deposition time to 20min to obtain a film with a thickness of 1.6μm. The titanium dioxide prefabricated thin film has a grain size of 50nm, and then a prefabricated energy storage ceramic thin film is obtained.

Turn off the magnetron sputtering power supply and the argon gas valve, increase the argon gas flow rate to 180sccm, make the vacuum degree of the vacuum chamber 0.8Pa, heat the temperature to 350°C, and hold for 4h to eliminate the residual stress of the prefabricated energy storage ceramic film, An energy storage ceramic thin film is obtained. The energy storage ceramic thin film includes copper foil and sequentially formed on the copper foil are a copper layer, a copper-titanium alloy layer, a titanium layer, a titanium dioxide layer and a titanium dioxide film, wherein the titanium dioxide layer and the titanium dioxide film constitute the ceramic film.

Copper metal was deposited on the titanium dioxide film of the energy storage film as an upper electrode through a magnetron sputtering process, and the electrical performance test was carried out.

After testing, the thickness of the titanium dioxide film in the energy storage ceramic film is 1.2 μm, the grain size of the titanium dioxide film is 100 nm, the thickness of the titanium dioxide layer is 8 nm, the thickness of the titanium layer is 46 nm, the thickness of the copper-titanium alloy layer is 10 nm, and the copper layer The thickness of the layer is 20nm, and the binding force between each layer is 5B. The energy storage ceramic thin film is flexible, the minimum bending radius is 8 mm, the breakdown field strength is 3000 kV/cm, and the energy storage density is 40 J/cm ³ . After 1000 times of bending, the binding force between each layer is 5B, the energy storage density is 39.8J/cm ³ , and the retention rate is 99.5%, which can be applied in film capacitors.

The technical features of the above-mentioned embodiments can be combined arbitrarily. To make the description concise, all possible combinations of the technical features in the above-mentioned embodiments are not described. However, as long as there is no contradiction in the combination of these technical features, should be considered as within the scope of this specification.

The above-mentioned embodiments only express several implementation modes of the present invention, and the descriptions thereof are relatively specific and detailed, but should not be construed as limiting the patent scope of the invention. It should be pointed out that those skilled in the art can make several modifications and improvements without departing from the concept of the present invention, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the patent for the present invention should be based on the appended claims.

Claims (10)

1. An energy storage ceramic thin film, characterized in that the energy storage ceramic thin film comprises a metal substrate and a first metal layer, a second metal layer, and a second metal oxide layer sequentially formed on the metal substrate and a second metal oxide thin film; Wherein, the material of the first metal layer is the same as that of the metal substrate; The surface of the first metal layer is also provided with an alloy layer formed by combining the second metal in the second metal layer with the first metal in the first metal layer; The second metal oxide layer is obtained by in-situ growth of the second metal layer, the second metal layer includes a titanium layer, the second metal oxide layer includes a titanium dioxide layer, and the second metal oxide thin film Including titanium dioxide film. 2. The energy storage ceramic thin film according to claim 1, characterized in that, the first metal layer and the second metal layer are formed by depositing and forming the first metal layer and the second metal layer by using a magnetic filter multi-arc ion plating method, When forming the second metal layer by deposition, the first metal in the first metal layer and the second metal in the second metal layer form the alloy layer. 3 . The energy storage ceramic thin film according to claim 1 , wherein the surface roughness of the metal substrate is 10 nm to 400 nm. 4 . 4. The energy storage ceramic film according to claim 1, wherein the metal substrate has a thickness of 6 μm to 18 μm; and/or The surface tension of the metal substrate is greater than or equal to 60 dynes. 5 . The energy storage ceramic thin film according to claim 1 , wherein the thickness of the first metal layer is 20nm-40nm. 6 . The energy storage ceramic thin film according to claim 1 , wherein the thickness of the second metal layer is 30nm-60nm. 7 . The energy storage ceramic thin film according to claim 1 , wherein the alloy layer has a thickness of 5 nm to 10 nm. 8 . The energy storage ceramic thin film according to claim 1 , wherein the thickness of the second metal oxide layer is 5 nm˜10 nm. 9. The energy storage ceramic thin film according to claim 1, characterized in that, the thickness of the second metal oxide thin film is 25nm-1.99μm, and the grain size of the second metal oxide thin film is 30nm-300nm . 10. The energy storage ceramic film according to claim 1, wherein the metal substrate comprises copper foil, the first metal layer comprises a copper layer, and the alloy layer comprises a copper-titanium alloy layer.

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